Deodorizing preparations containing nanosacle chitosans and/or chitosan derivatives

ABSTRACT

The invention relates to novel deodorizing preparations that contain nanoscale chitosans and/or chitosan derivatives.

FIELD OF THE INVENTION

[0001] This invention relates generally to cosmetic preparations andmore particularly to the use of nanoscale chitosans and/or chitosanderivatives in deodorizing preparations.

PRIOR ART

[0002] In the field of personal care, deodorants are used to eliminateunpleasant body odors. Typical examples of such substances are aluminiumcompounds, such as aluminium sulfate or aluminium chlorohydrate, zincsalts and citric acid compounds. Since the problem of odor inhibitionhas by no means been completely solved, there is still a need for newpreparations which contain dermatologically compatible deodorants with along-lasting effect.

[0003] It is known from DE 19540296C2 that chitosans inhibit theactivity of esterase-producing bacteria and that a synergisticdeodorizing effect is obtained together with esterase inhibitors andaluminium chlorohydrates. The chitosans have a bacteriostatic effect,i.e. the population of the particular germs is controlled but not killedoff in order not to impair the biological equilibrium of the skin flora.The effect of the chitosans or chitosan derivatives and its duration arealways associated with the rate at which the compounds are incorporatedand absorbed. So far as the compounds hitherto available are concerned,there is considerable potential for improvement in this regard.

[0004] The general use of water-soluble chitosan salts in deodorants andantibacterial cosmetics is claimed in Japanese patent application JP63290808. However, there is a need to further improve the antibacterialactivity of chitosans by special formulations.

[0005] “Nanonized material” in the context of the present invention isunderstood to mean spherical aggregates with a diameter of about 1 toabout 500 nm which contain at least one solid or liquid core surroundedby at least one continuous membrane. Their use in cosmetics wasdescribed in 1997 by Zülli, F. and Suter, F. (Preparation and Propertiesof Small Nanoparticles for Skin and Hair Care, Seifen-Öle-Fette-Wachse123 (1997), No. 13, p. 880, 883-885) and by Mehnert, W. et al. (SolidLipid Nanoparticles, A Novel Carrier for Cosmetics and Pharmaceuticals,Pharm. Ind. 59 (1997), pp. 511-514). The core and membrane may consistof one and the same material or even of different materials.

[0006] The processing of auxiliaries and active substances in selectedformulations can be simplified by using them in the form ofnanoparticles. This applies above all where there is incompatibilitywith other auxiliaries. In addition, the release and absorption ofsubstances can be controlled through the particle or capsule size, bythe use of various auxiliaries or various physicochemical properties.

[0007] U.S. Pat. No. 5,194,262 and U.S. Pat. No. 5,271,934 describemicrocapsules containing antiperspirants. These microcapsules acquirebioadhesive properties through constituents of the membrane or evenadditional coatings and thus contribute to a long-lasting effect.

[0008] Accordingly, the problem addressed by the invention was toimprove the distribution and uptake of chitosans or chitosan derivativesand at the biopolymers would lend themselves to simple incorporation inthe formulation and their compatibility with anionic auxiliaries wouldbe improved. The final formulation would be distinguished by a pleasantskin feel, high dermatological compatibility and high stability.

DESCRIPTION OF THE INVENTION

[0009] The present invention relates to deodorizing preparations whichcontain nanoscale chitosans and/or chitosan derivatives with a particlediameter in the range from 10 to 300 nm.

[0010] It has surprisingly been found that the use of nanoscale chitosanleads to a long-lasting deodorizing effect, that the absorption ofchitosans or chitosan derivatives by the Stratum corneum of the skin canbe increased and that, in addition, the production of the preparationsand their compatibility with anionic surfactants are considerablyfacilitated by the use of the nanoscale chitosans. The formulationsproduced have a pleasant feeling on the skin and show high stability.The moisturizing effect of “nanochitosans” counteracts possible dryingout of the skin, particularly in the case of alcohol-containing aerosolformulations.

[0011] Chitosans and Chitosan Derivatives

[0012] Chitosans are biopolymers which belong to the group ofhydrocolloids. Chemically, they are partly deacetylated chitins varyingin molecular weight which contain the idealized monomer unit:

[0013] Chitosans are produced from chitin, preferably from the shellremains of crustaceans which are available in large quantities asinexpensive raw materials. Normally, the chitin is first deproteinizedby addition of bases, demineralized by addition of mineral acids and,finally, deacetylated by addition of strong bases in a process describedfor the first time by Hackmann et al., the molecular weights beingspread over a broad range. Corresponding processes are known, forexample, from Makromol. Chem. 177, 3589 (1976) or French patentapplication FR 2701266 Al. Preferred types are those described in Germanpatent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) which havean average molecular weight of 800,000 to 1,200,000 dalton, a Brookfieldviscosity (1% by weight in glycolic acid) below 5,000 mPas, a degree ofdeacetylation of 80 to 88% and an ash content of less than 0.3% byweight. Besides chitosans as typical cationic biopolymers, anionically,nonionically or cationically derivatized chitosans, for example thecarboxylation, succinylation, alkoxylation or quaternization productsdescribed, for example, in German patent DE 3713099 C2 (L”Oreal) and inGerman patent application DE 19604180 A1 (Henkel), may also be used.

[0014] Production of Nanoparticles

[0015] One process for the production of nanoparticles by rapidexpansion of supercritical solutions (RESS process) is known from thearticle by S. Chihiar, M. Türk and K. Schaber in Proceedings WorldCongress on Particle Technology 3, Brighton, 1998. A preferredembodiment of the invention is characterized by the use of nanoscalechitosans and/or chitosan derivatives obtained by

[0016] (a) dissolving the starting materials in a suitable solvent undersupercritical or near-critical conditions,

[0017] (b) expanding the fluid mixture through a nozzle into a vacuum, agas or a liquid and

[0018] (c) simultaneously evaporating the solvent.

[0019] To prevent the nanoparticles from agglomerating, it is advisableto dissolve the starting materials in the presence of suitableprotective colloids or emulsifiers and/or to expand the criticalsolutions into aqueous and/or alcoholic solutions of the protectivecolloids or emulsifiers or into cosmetic oils which may in turn containredissolved emulsifiers and/or protective colloids. Suitable protectivecolloids are, for example, gelatine, casein, gum arabic, lysalbinicacid, starch and polymers, such as polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene glycols and polyacrylates. Accordingly, thenanoscale chitosans and/or chitosan derivatives preferably used arethose which are surrounded by a protective colloid and/or an emulsifier.The protective colloids or emulsifiers are normally used in quantitiesof 0.1 to 20% by weight and preferably in quantities of 5 to 15% byweight, based on the chitosans and/or chitosan derivatives.

[0020] Another suitable process for the production of nanoscaleparticles is the evaporation technique. Here, the chitosans aredissolved in a suitable dilute organic acid or mineral acid, for exampleglycolic acid, lactic acid or hydrochloric acid at pH values of 1 to 5.The resulting solution is introduced into a nonsolvent for the chitosans(for example alkanes, vegetable oils, cosmetic oils, ethers, esters,ketones, acetals and the like) which may contain a surface-activecompound. As a result of the mixing of the two systems, thenanoparticles are precipitated, the aqueous phase preferablyevaporating. W/o or o/w microemulsions may be used instead of theaqueous solutions and mixed with the nonsolvent. The emulsifiers andprotective colloids mentioned at the beginning may be used as thesurface-active compounds. Another method for the production ofnanoparticles is the so-called GAS process (gas anti-solventrecrystallization). This process uses a highly compressed gas orsupercritical fluid (for example carbon dioxide) as non-solvent for thecrystallization of dissolved substances. The compressed gas phase isintroduced into the primary solution of the starting materials andabsorbed therein so that there is an increase in the liquid volume and areduction in solubility and fine particles are precipitated. The PCAprocess (precipitation with a compressed fluid anti-solvent) is equallysuitable. In this process, the primary solution of the startingmaterials is introduced into a supercritical fluid which results in theformation of very fine droplets in which diffusion processes take placeso that very fine particles are precipitated. In the PGSS process(particles from gas saturated solutions), the starting materials aremelted by the introduction of gas under pressure (for example carbondioxide or propane). Temperature and pressure reach near- orsuper-critical conditions. The gas phase dissolves in the solid andlowers the melting temperature, the viscosity and the surface tension.On expansion through a nozzle, very fine particles are formed as aresult of cooling effects.

[0021] Commercial Applications

[0022] Compared with conventional chitosans and/or chitosan derivatives,the particular fineness of the particles provides for their more rapidpenetration into the stratum corneum after topical application. On theother hand, a long-lasting deodorizing effect is also obtained throughthe slow dissolution of the particles at the point of action. Thenanoscale compounds are normally used in a quantity of 0.01 to 5% byweight, preferably in a quantity of 0.1 to 1% by weight and moreparticularly in a quantity of 0.2 to 0.6% by weight, based on thepreparations.

[0023] The mean particle sizes (volume distribution) of the nanoparticleused are in the range from 1 to 300 nm, preferably in the range from 10to 200 nm and more particularly in the range from 50 to 150 nm. Thedeodorant preparations, such as creams, gels, roll-on, sticks andsprays, obtainable using the nanoscale chitosans and chitosanderivatives in accordance with the invention may additionally containmild surfactants, oil components, emulsifiers, superfatting agents,stabilizers, consistency factors, thickeners, polymers, siliconecompounds, biogenic agents, preservatives, hydrotropes, solubilizers,antioxidants, propellent gases, perfume oils, dyes and the like asfurther auxiliaries and additives.

[0024] Antiperspirants

[0025] The antiperspirants of component (b1) are salts of aluminium,zirconium or zinc. Suitable antihydrotic agents of this type are, forexample, aluminium chloride, aluminium chlorohydrate, aluminiumdichlorohydrate, aluminium sesquichlorohydrate and complex compoundsthereof, for example with 1,2-propylene glycol, aluminiumhydroxy-allantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof, for examplewith amino acids, such as glycine. Aluminium chlorohydrate, aluminiumzirconium tetrachlorohydrate, aluminium zirconium pentachlorohydrate andcomplex compounds thereof are preferably used. In addition,antiperspirants may contain typical oil-soluble and water-solubleauxiliaries in relatively small amounts. Oil-soluble auxiliaries such asthese include, for example,

[0026] inflammation-inhibiting, skin-protecting or pleasant-smellingessential oils,

[0027] synthetic skin-protecting agents and/or

[0028] oil-soluble perfume oils.

[0029] The preparations according to the invention may contain theantiperspirants in quantities of 1 to 50, preferably 5 to 30 and moreparticularly 10 to 25% by weight, based on the solids content.

[0030] Esterase Inhibitors

[0031] Where perspiration is present in the underarm region,extracellular enzymes—esterases, mainly proteases and/or lipases—areformed by bacteria and split the esters present in the perspiration,releasing odors in the process. Esterase inhibitors of component . . .are preferably trialkyl citrates, such as trimethyl citrate, tripropylcitrate, triisopropyl citrate, tributyl citrate and, in particular,triethyl citrate (Hydagen® CAT, Cognis GmbH, Düsseldorf, FRG). Esteraseinhibitors inhibit enzyme activity and thus reduce odor formation. Thefree acid is probably released by the cleavage of the citric acid esterand reduces the pH value of the skin to such an extent that the enzymesare inactivated by acylation. Other esterase inhibitors are sterolsulfates or phosphates such as, for example, lanosterol, cholesterol,campesterol, stigmasterol and sitosterol sulfate or phosphate,dicarboxylic acids and esters thereof, for example glutaric acid,glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid,adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid andmalonic acid diethyl ester, hydroxycarboxylic acids and esters thereof,for example citric acid, malic acid, tartaric acid or tartaric aciddiethyl ester, and zinc glycinate.

[0032] The preparations according to the invention may contain theesterase inhibitors in quantities of 0.01 to 20, preferably 0.1 to 10and more particularly 0.5 to 5% by weight, based on the solids content.

[0033] Bactericidal or bacteriostatic agents

[0034] A typical example of an additional suitable bactericidal orbacteriostatic agent is phenoxyethanol.5-Chloro-2-(2,4-dichlorophenoxy)-phenol which is marketed under the nameof Irgasan® by Ciba-Geigy, Basle, Switzerland, has also proved to beparticularly effective.

[0035] The preparation according to the invention may contain thebactericidal or bacteriostatic agents in quantities of 0.01 to 5 andpreferably 0.1 to 2% by weight, based on the solids content.

[0036] Perspiration absorbers

[0037] Suitable perspiration absorbers are modified starch such as, forexample, Dry Flo Plus (National Starch), silicates, talcum and othersubstances of similar modification which appear suitable for absorbingperspiration.

[0038] The preparations according to the invention may contain theperspiration-absorbing substances in quantities of 0.1 to 30% by weight,preferably 1 to 20% by weight and more particularly 5 to 10% by weight,based on the solids content.

[0039] Other auxiliaries and additives

[0040] In order to be able to apply the active components to the skin ina measurable, economical, convenient and cosmetically attractive manner,they are normally incorporated in formulation bases (for typicalingredients, see below). The most important bases include alcoholic andaqueous/alcoholic solutions, emulsions, gels, oils, wax/fat compounds,stick preparations and powders. Other ingredients are superfattingagents, emulsifiers, antioxidants and perfume oils, essential oils, dyesand —for spray applications—propellent gases, such as propane and/orbutane for example. The preparations are preferably marketed as rollers(roll-on emulsions), sticks, creams, deodorant or pump sprays.

[0041] These preparations may contain mild surfactants, consistencyfactors, thickeners, stabilizers, polymers, silicone compounds, fats,waxes, lecithins, phospholipids, biogenic agents, film formers,solubilizers, preservatives, dyes and the like as further auxiliariesand additives.

[0042] Surfactants

[0043] Suitable surfactants are anionic, nonionic, cationic and/oramphoteric or zwitterionic surfactants which may be present in thepreparations in quantities of normally about 1 to 70% by weight,preferably 5 to 50% by weight and more preferably 10 to 30% by weight.Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkylethersulfonates, glycerol ether sulfonates, α-methyl ester sulfonates,sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerolether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates,monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono-and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates,sulfotriglycerides, amide soaps, ether carboxylic acids and saltsthereof, fatty acid isethionates, fatty acid sarcosinates, fatty acidtaurides, N-acylamino acids such as, for example, acyl lactylates, acyltartrates, acyl glutamates and acyl aspartates, alkyl oligoglucosidesulfates, protein fatty acid condensates (particularly wheat-basedvegetable products) and alkyl (ether) phosphates. If the anionicsurfactants contain polyglycol ether chains, they may have aconventional homolog distribution although they preferably have anarrow-range homolog distribution. Typical examples of nonionicsurfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycolethers, fatty acid polyglycol esters, fatty acid amide polyglycolethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixedethers and mixed formals, optionally partly oxidized alk(en)yloligoglycosides or glucuronic acid derivatives, fatty acid-N-alkylglucamides, protein hydrolyzates (particularly wheat-based vegetableproducts), polyol fatty acid esters, sugar esters, sorbitan esters,polysorbates and amine oxides. If the nonionic surfactants containpolyglycol ether chains, they may have a conventional homologdistribution, although they preferably have a narrow-range homologdistribution. Typical examples of cationic surfactants are quaternaryammonium compounds, for example dimethyl distearyl ammonium chloride,and esterquats, more particularly quaternized fatty acid trialkanolamineester salts. Typical examples of amphoteric or zwitterionic surfactantsare alkylbetaines, alkylamidobetaines, aminopropionates,aminoglycinates, imidazolinium betaines and sulfobetaines. Thesurfactants mentioned are all known compounds. Information on theirstructure and production can be found in relevant synoptic works, cf.for example J. Falbe (ed.), “Surfactants in Consumer Products”, SpringerVerlag, Berlin, 1987, pages 54 to 124 or J. Falbe (ed.), “Katalysatoren,Tenside und Mineraloladditive (Catalysts, Surfactants and Mineral OilAdditives)”, Thieme Verlag, Stuttgart, 1978, pages 123-217. Typicalexamples of particularly suitable mild, i.e. particularlydermatologically compatible, surfactants are fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines, amphoacetals and/or protein fatty acid condensates,preferably based on wheat proteins.

[0044] Oil Components

[0045] Suitable oil components are, for example, Guerbet alcohols basedon fatty alcohols containing 6 to 18 and preferably 8 to 10 carbonatoms, esters of linear C₆₋₂₂ fatty acids with linear C₆₋₂₂ fattyalcohols, esters of branched C6-13 carboxylic acids with linear C₆₋₂₂fatty alcohols such as, for example, myristyl myristate, myristylpalmitate, myristyl stearate, myristyl isostearate, myristyl oleate,myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate,cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetylerucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearylisostearate, stearyl oleate, stearyl behenate, stearyl erucate,isostearyl myristate, isostearyl palmitate, isostearyl stearate,isostearyl isostearate, isostearyl oleate, isostearyl behenate,isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate,oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenylmyristate, behenyl palmitate, behenyl stearate, behenyl isostearate,behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate,erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate,erucyl behenate and erucyl erucate. Also suitable are esters of linearC₆₋₂₂ fatty acids with branched alcohols, more particularly 2-ethylhexanol, esters of C₁₈₋₃₈ alkylhydroxycarboxylic acids with linear orbranched C₆₋₂₂ fatty alcohols (cf. DE 197 56 377 A1), more especiallyDioctyl Malate, dialkyl carbonates including, in particular, dioctylcarbonate, esters of linear and/or branched fatty acids with polyhydricalcohols (for example propylene glycol, dimer diol or trimer triol)and/or Guerbet alcohols, triglycerides based on C₆₋₁₀ fatty acids,liquid mono-, di-and triglyceride mixtures based on C₆₋₁₈ fatty acids,esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols with aromaticcarboxylic acids, more particularly benzoic acid, esters of C₂₋₁₂dicarboxylic acids with linear or branched alcohols containing 1 to 22carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6hydroxyl groups, vegetable oils, branched primary alcohols, substitutedcyclohexanes, Guerbet carbonates, esters of benzoic acid with linearand/or branched C₆₋₂₂ alcohols (for example Finsolv® TN), linear orbranched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to22 carbon atoms per alkyl group, ring opening products of epoxidizedfatty acid esters with polyols, silicone oils (cyclomethicone, siliconmethicone types, etc.) and/or aliphatic or naphthenic hydrocarbons, forexample squalane, squalene or dialkyl cyclohexanes.

[0046] Emulsifiers

[0047] Suitable emulsifiers are, for example, nonionic surfactants fromat least one of the following groups:

[0048] products of the addition of 2 to 30 moles of ethylene oxideand/or 0 to 5 moles of propylene oxide onto linear C₈₋₂₂ fatty alcohols,C₁₂₋₂₂ fatty acids and alkyl phenols containing 8 to 15 carbon atoms inthe alkyl group and alkylamines containing 8 to 22 carbon atoms in thealkyl group;

[0049] alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbonatoms in the alkyl group and ethoxylated analogs thereof;

[0050] addition products of 1 to 15 moles of ethylene oxide onto castoroil and/or hydrogenated castor oil;

[0051] addition products of 15 to 60 moles of ethylene oxide onto castoroil and/or hydrogenated castor oil;

[0052] partial esters of glycerol and/or sorbitan with unsaturated,linear or saturated, branched fatty acids containing 12 to 22 carbonatoms and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms andadducts thereof with 1 to 30 moles of ethylene oxide;

[0053] partial esters of polyglycerol (average degree ofself-condensation 2 to 8), polyethylene glycol (molecular weight 400 to5,000), trimethylolpropane, pentaerythritol, sugar alcohols (for examplesorbitol), alkyl glucosides (for example methyl glucoside, butylglucoside, lauryl glucoside) and polyglucosides (for example cellulose)with saturated and/or unsaturated, linear or branched fatty acidscontaining 12 to 22 carbon atoms and/or hydroxycarboxylic acidscontaining 3 to 18 carbon atoms and adducts thereof with 1 to 30 molesof ethylene oxide;

[0054] mixed esters of pentaerythritol, fatty acids, citric acid andfatty alcohol according to DE 11 65 574 PS and/or mixed esters of fattyacids containing 6 to 22 carbon atoms, methyl glucose and polyols,preferably glycerol or polyglycerol,

[0055] mono-, di- and trialkyl phosphates and mono-, di- and/ortri-PEG-alkyl phosphates and salts thereof,

[0056] wool wax alcohols

[0057] polysiloxane/polyalkyl/polyether copolymers and correspondingderivatives,

[0058] block copolymers, for example Polyethyleneglycol-30Dipolyhydroxystearate;

[0059] polymer emulsifiers, for example Pemulen types (TR-1, TR-2) ofGoodrich;

[0060] polyalkylene glycols and

[0061] glycerol carbonate.

[0062] The addition products of ethylene oxide and/or propylene oxideonto fatty alcohols, fatty acids, alkylphenols or onto castor oil areknown commercially available products. They are homolog mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as refatting agents for cosmeticformulations from DE 20 24 051 PS.

[0063] Alkyl and/or alkenyl oligoglycosides, their production and theiruse are known from the prior art. They are produced in particular byreacting glucose or oligosaccharides with primary alcohols containing 8to 18 carbon atoms. So far as the glycoside unit is concerned, bothmonoglycosides in which a cyclic sugar unit is attached to the fattyalcohol by a glycoside bond and oligomeric glycosides with a degree ofoligomerization of preferably up to about 8 are suitable. The degree ofoligomerization is a statistical mean value on which the homologdistribution typical of such technical products is based.

[0064] Typical examples of suitable partial glycerides arehydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,isostearic acid monoglyceride, isostearic acid diglyceride, oleic acidmonoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride,ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic aciddiglyceride, linolenic acid monoglyceride, linolenic acid diglyceride,erucic acid monoglyceride, erucic acid diglyceride, tartaric acidmonoglyceride, tartaric acid diglyceride, citric acid monoglyceride,citric acid diglyceride, malic acid monoglyceride, malic aciddiglyceride and technical mixtures thereof which may still contain smallquantities of triglyceride from the production process. Additionproducts of 1 to 30 and preferably 5 to 10 moles of ethylene oxide ontothe partial glycerides mentioned are also suitable.

[0065] Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30 and preferably 5 to 10 moles of ethyleneoxide with the sorbitan esters mentioned are also suitable.

[0066] Typical examples of suitable polyglycerol esters arePolyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH),Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate(Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3Diisostearate (Isolan® PDI), Poly-glyceryl-3 Methylglucose Distearate(Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether(Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) andPolyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl DimerateIsostearate and mixtures thereof. Examples of other suitablepolyolesters are the mono-, di- and triesters of trimethylolpropane orpentaerythritol with lauric acid, cocofatty acid, tallow fatty acid,palmitic acid, stearic acid, oleic acid, behenic acid and the likeoptionally reacted with 1 to 30 moles of ethylene oxide.

[0067] Other suitable emulsifiers are zwitterionic surfactants.Zwitterionic surfactants are surface-active compounds which contain atleast one quaternary ammonium group and at least one carboxylate and onesulfonate group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C12/18 acyl sarcosine. Finally,cationic surfactants are also suitable emulsifiers, those of theesterquat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

[0068] Fats and waxes

[0069] Typical examples of fats are glycerides, i.e. solid or liquid,vegetable or animal products which consist essentially of mixed glycerolesters of higher fatty acids. Suitable waxes are inter alia naturalwaxes such as, for example, candelilla wax, carnauba wax, Japan wax,espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax,ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin(wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum,paraffin waxes and microwaxes; chemically modified waxes (hard waxes)such as, for example, montan ester waxes, sasol waxes, hydrogenatedjojoba waxes and synthetic waxes such as, for example, polyalkylenewaxes and polyethylene glycol waxes. Besides the fats, other suitableadditives are fat-like substances, such as lecithins and phospholipids.Lecithins are known among experts as glycerophospholipids which areformed from fatty acids, glycerol, phosphoric acid and choline byesterification. Accordingly, lecithins are also frequently referred toby experts as phosphatidyl cholines (PCs) and correspond to thefollowing general formula:

[0070] where R typically represents linear aliphatic hydrocarbonradicals containing 15 to 17 carbon atoms and up to 4 cis-double bonds.Examples of natural lecithins are the kephalins which are also known asphosphatidic acids and which are derivatives of1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipidsare generally understood to be mono- and preferably diesters ofphosphoric acid with glycerol (glycerophosphates) which are normallyclassed as fats. Sphingosines and sphingolipids are also suitable.

[0071] Consistency factors and thickeners

[0072] The consistency factors mainly used are fatty alcohols orhydroxyfatty alcohols containing 12 to 22 and preferably 16 to 18 carbonatoms and also partial glycerides, fatty acids or hydroxyfatty acids. Acombination of these substances with alkyl oligoglucosides and/or fattyacid N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used. Suitable thickeners are,for example, Aerosil® types (hydrophilic silicas), polysaccharides, moreespecially xanthan gum, guar-guar, agar-agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl cellulose, also relatively highmolecular weight polyethylene glycol monoesters and diesters of fattyacids, polyacrylates (for example Carbopols® and Pemulen types[Goodrich]; Synthalens® [Sigma]; Keltrol types [Kelco]; Sepigel types[Seppic]; Salcare types [Allied Colloids]), polyacrylamides, polymers,polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, forexample, ethoxylated fatty acid glycerides, esters of fatty acids withpolyols, for example pentaerythritol or trimethylol propane,narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides andelectrolytes, such as sodium chloride and ammonium chloride.

[0073] Superfatting Agents

[0074] Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin 20 and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

[0075] Stabilizers

[0076] Metal salts of fatty acids such as, for example, magnesium,aluminium and/or zinc stearate or ricinoleate may be used asstabilizers.

[0077] Polymers

[0078] Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, forexample, Luviquat® (BASF), condensation products of polyglycols andamines, quaternized collagen polypeptides such as, for example,Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau),quaternized wheat polypeptides, polyethyleneimine, cationic siliconepolymers such as, for example, Amodimethicone, copolymers of adipic acidand dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine®,Sandoz), copolymers of acrylic acid with dimethyl diallyl ammoniumchloride (Merquat® 550, Chemviron), polyaminopolyamides as described,for example, in FR 2 252 840 A and crosslinked water-soluble polymersthereof, cationic chitin derivatives such as, for example, quaternizedchitosan, optionally in micro-crystalline distribution, condensationproducts of dihaloalkyls, for example dibromobutane, withbis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationicguar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 ofCelanese, quaternized ammonium salt polymers such as, for example,Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

[0079] Suitable anionic, zwitterionic, amphoteric and nonionic polymersare, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinylether/maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamido-propyltrimethylammonium chloride/acrylate copolymers, octylacryl-amide/methylmethacrylate/tert.-butylaminoethyl methacrylate/2-hydroxy-propylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers, vinyl pyrrolidone/dimethylaminoethylmethacrylate/vinyl caprolactam terpolymers and optionally derivatizedcellulose ethers and silicones. Other suitable polymers and thickenerscan be found in Cosmetics & Toiletries, Vol. 108, May 1993, pages 95 etseq.

[0080] Silicone Compounds

[0081] Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-,fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.A detailed overview of suitable volatile silicones can be found in Toddet al. in Cosm. Toil. 91, 27 (1976).

[0082] Biogenic Agents

[0083] In the context of the invention, biogenic agents are, forexample, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbicacid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol,panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essentialoils, plant extracts and vitamin complexes.

[0084] Additional Deodorants and Germ Inhibitors

[0085] Cosmetic deodorants counteract, mask or eliminate body odors.Body odors are formed through the action of skin bacteria on apocrineperspiration which results in the formation of unpleasant-smellingdegradation products. Accordingly, deodorants contain active principleswhich act as germ inhibitors, enzyme inhibitors, odor absorbers or odormaskers. Basically, suitable germ inhibitors are any substances whichact against gram-positive bacteria such as, for example,4-hydroxybenzoic acid and salts and esters thereof,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea,2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan),4-chloro-3,5dimethylphenol, 2,2′-methylene-bis-(6-bromo4-chlorophenol),3-methyl4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialperfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylicacid-N-alkylamides such as, for example, salicylic acid-n-octyl amide orsalicylic acid-n-decyl amide. The percentage content of the additionalgerm inhibitors is about 0.1 to 2% by weight, based on the percentagesolids content of the preparations.

[0086] Suitable odor absorbers are substances which are capable ofabsorbing and largely retaining the odor-forming compounds. They reducethe partial pressure of the individual components and thus also reducethe rate at which they spread. An important requirement in this regardis that perfumes must remain unimpaired. Odor absorbers are not activeagainst bacteria. They contain, for example, a complex zinc salt ofricinoleic acid or special perfumes of largely neutral odor known to theexpert as “fixateurs” such as, for example, extracts of ladanum orstyrax or certain abietic acid derivatives as their principal component.Odor maskers are perfumes or perfume oils which, besides theirodor-masking function, impart their particular perfume note to thedeodorants. Suitable perfume oils are, for example, mixtures of naturaland synthetic perfumes. Natural perfumes include the extracts ofblossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs andgrasses, needles and branches, resins and balsams. Animal raw materials,for example civet and beaver, may also be used. Typical syntheticperfume compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Examples of perfume compounds of the estertype are benzyl acetate, p-tert.butyl cyclohexylacetate, linalylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.Ethers include, for example, benzyl ethyl ether while aldehydes include,for example, the linear alkanals containing 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxy-citronellal, lilial and bourgeonal. Examples of suitable ketonesare the ionones and methyl cedryl ketone. Suitable alcohols are anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol. The hydrocarbons mainly include the terpenes andbalsams. However, it is preferred to use mixtures of different perfumecompounds which, together, produce an agreeable fragrance. Othersuitable perfume oils are essential oils of relatively low volatilitywhich are mostly used as aroma components. Examples are sage oil,camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil, ladanum oil and lavendin oil. The following are preferably usedeither individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romilat, irotyl and floramat.

[0087] Preservatives

[0088] Suitable preservatives are, for example, phenoxyethanol,formaldehyde solution, parabens, pentanediol or sorbic acid and theother classes of compounds listed in Appendix 6, Parts A and B of theKosmetikverordnung (“Cosmetics Directive”).

[0089] Perfume oils

[0090] Suitable perfume oils are mixtures of natural and syntheticfragrances. Natural fragrances include the extracts of blossoms (lily,lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves(geranium, patchouli, petitgrain), fruits (anise, coriander, caraway,juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica,celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood,guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, dwarfpine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,opoponax). Animal raw materials, for example civet and beaver, may alsobe used. Typical synthetic perfume compounds are products of the ester,ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples ofperfume compounds of the ester type are benzyl acetate, phenoxyethylisobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-citronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,α-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeablefragrance. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

[0091] Dyes

[0092] Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.These dyes are normally used in concentrations of 0.001 to 0.1% byweight, based on the mixture as a whole.

Examples

[0093] Preparation of the Nanoscale Chitosans and Chitosan Derivatives

[0094] In Examples 1 and 2, carbon dioxide was first taken from areservoir under a constant pressure of 60 bar and was purified in acolumn with an active carbon and a molecular sieve packing. Afterliquefaction, the CO₂ was compressed to the required supercriticalpressure p by a diaphragm pump at a constant delivery rate of 3.5 l/h.The solvent was then brought to the necessary temperature T1 in apreheater and was introduced into an extraction column (steel, 400 ml)charged with the chitosan or chitosan derivative. The resultingsupercritical, i.e. fluid, mixture was sprayed through a laser-drawnnozzle (length 830 μm, diameter 45 pm) at a temperature T2 into aPlexiglas expansion chamber containing a 4% by weight aqueous solutionof an emulsifier or protective colloid. The fluid medium evaporated,leaving the dispersed nanoparticles encapsulated in the protectivecolloid behind. The process conditions and the average particle sizerange (PSR, as determined photometrically by the 3-WEM method) are setout in Table 1 below. TABLE 1 Production parameters for nanoparticlesEmulsifier/ Chitosan p T1 T2 Protective PSR Ex. (derivative) Solv. bar °C. ° C. Colloid nm 1 Chitosan CO₂ 200 85 180 Polyvinyl 70-140 alcohol 2Chitosan CO₂ 200 85 175 Polyvinyl 50-150 Succinate alcohol

[0095] TABLE 2a Antiperspirant or deodorant suspension sticks and softsolids - quantities = % by weight Composition 1 2 3 4 5 6 Nanochitosanof   0.1   0.2   0.4   0.6 0.3   0.5 Example 1 in Table 1 Distearylether − 15 − − − − Stearyl alcohol − − 10 10 14.7  − Guerbet alcohol 15− − − − − C36 Tribehenin − − − − − 20 Hyrogenated − − − − 3.7 − CastorOil Dioctyl 20 60 60 60 58.7  55 carbonate Octyl dodecanol 10 − − − − −Dicaprylyl ether 10 − − − − Hexyl decanol + 10 − − − − − HexyldecylLaurate Cyclomethicone 10 − − − − − Dry Flo Plus* − −  5 − − − Silica −− −   2.5 − Talcum − − −   2.5 − − Aluminium − − 25 − − − ZirconiumTetra- chlorohydrex GLY Aluminium 25 − − − − − Chlorohydrate Rub-offcolor White White White White White White Hardness**   4.2   4.2   5.0  4.9 4.2   4.6 Oil secretion No No No No No No Feeling on theParticularly Particularly Particularly Particularly Particularly Soft,skin velvety, velvety, velvety, soft, velvety, soft, velvety, creamy,soft, soft, powdery, powdery, soft, powdery powdery, powdery,particularly particularly powdery, dry dry dry, not oily dry dry atbeginning

[0096] TABLE 2b Antiperspirant or deodorant suspension sticks and softsolids - quantities = % by weight Composition 7 8 9 10 11 Nanochitosanof   0.4   0.3   0.5   0.2   0.2 Example 2 in Table 1 12-Hydroxy- 10  5 8 − 10 stearic acid Dibutyl Lauroyl − −  2 − − Glutamide Distearylether − − − Stearyl alcohol − − − 18 − Tribehenin − − − − − Hydrogenated− − −  5 − Castor Oil Dioctyl Carbonate 65 65 65 − − Octyl dodecanol − −− 15 15 Cyclomethicone − − − 37 50 Dry Flo Plus* −  5 − − − Silica − − −− − Talcum − − − − − Aluminium − 25 Zirconium Tetra- chlorohydrex GLYAluminium − − − 25 − Chlorohydrate Rub-off color Transparent TransparentTransparent Strong white Transparent Hardness**   4.0   5.0   4.0   4.1  4.0 Oil secretion No No No No No Feeling on the ParticularlyParticularly Particularly Wax- Soft, slightly skin velvety, soft,velvety, soft, velvety, soft, like, dry powdery powdery, powdery,powdery, dry dry particularly dry, not oily at beginning

[0097] The emulsification properties and stability of the preparationsaccording to the invention were subjectively evaluated (+=very good,−=satisfactory). TABLE 3 Deodorant creams - quantities in % by weightComposition 1 2 3 4 Nanochitosan of Example 1 0.2 0.2 0.2 0.2 in Table 1Emulgade SE-PF* 6.0 6.0 6.0 6.0 Sodium Cetearyl Sulfate 0.5 0.5 0.5 0.5Cetearyl alcohol 1   1   − − Behenyl alcohol 3   3   4   4   Dioctylcarbonate 6.0 3   9.0 9.0 Cyclomethicone 3.0 2   − − Octyl dodecanol −1   − − Dicaprylyl ether − 2   − − Hexyldecanol + Hexyldecyl − 1   − −Laurate Farnesol − − − 0.2 Triethyl citrate − − − 1.5 Talcum − 10.0 10.0  − Water, demin. to to to to Emulsification properties + + + +Homogeneous distribution + + + + of active principle Stability + + + +Feeling on the skin Very Very Particularly Very velvety, velvety,velvety, soft, velvety, soft soft powdery soft and caring

[0098] The emulsification properties and stability of the preparationsaccording to the invention were subjectively evaluated (+=very good,−=satisfactory). TABLE 3 Oil-in-water emulsions for roll-on andsprayable antiperspirant/ deodorant applications - quantities in % byweight Composition 1 2 3 4 Nanochitosan of 0.1   0.1 0.3 0.1 Example 2in Table 1 Emulgade SE-PF* 4.1   4.1 − − Ceteareth-20 0.9   0.9 1.5 1.5Ceteareth-10 − − 1.5 1.5 Glyceryl Stearate − − 5.0 5.0 Cetyl Alcohol − −3.0 3.0 Dioctyl carbonate 10.0  3 3.0 3.0 Cyclomethicone − 2 − − Octyldodecanol − 2 − − Dicaprylyl ether − 2 − − Hexyl decanol + − 1 − −Hexyldecyl Laurate Triethyl citrate − − − 0.5 Water, demin. to 100 to100 to 100 to 100 Emulsification + + + + properties Stability + + + +Feeling on the skin Quickly Quickly Less caring, Quickly absorbed,absorbed, less dry absorbed, fairly dry fairly dry skin feel fairly drycaring caring caring skin feel skin feel skin feel

[0099] TABLE 5 Deodorant aerosol applications - quantities in % byweight Composition 1 2 3 4 5 6 Nanochitosan of Example 2 0.2 0.4 0.1 0.10.1 0.1 in Table 1 LPG 2,7 45 50 48 50 Drivosol 3,5 40 45 Isopentane 2020 10 20 25 Diethyl ether 5 5 5 Isopropyl palmitate 15 − − − 10 12Dicapryl ether − 18 − − − 7.9 Hexyl decanol + hexyl decyl − − 15 − − −laurate Squalane − − − 10 − − Ethanol 20 15 − − Isopropanol − − 20 15 −− Cyclomethicone 4.8 1.6 4.9 9.9 4.9 − Aluminium Zirconium Tetra- − − 5− − − chlorohydrex GLY Aluminium Chlorohydrate − − − 5 − − TriethylCitrate − − − − 2 − Talcum − − − − 10 5 Emulsificationproperties + + + + + + Stability + + + + + + Skin feel + + + + + +

1. Deodorizing preparations containing nanoscale chitosans and/orchitosan derivatives with particle diameters of 10 to 300 nm. 2.Preparations as claimed in claim 1, characterized in that they containchitosans with a molecular weight of 50,000 to 2,000,000. 3.Preparations as claimed in claims 1 and 2, characterized in that theycontain anionically, nonionically or cationically derivatized chitosans.4. Preparations as claimed in at least one of claims 1 to 3,characterized in that they contain 0.01 to 5% by weight of nanoscalechitosans and/or chitosan derivatives with particle diameters of 10 to300 nm.
 5. Preparations as claimed in at least one of claims 1 to 4,characterized in that they contain other auxiliaries selected from thegroup consisting of esterase inhibitors, bactericidal or bacteriostaticagents, oil components, antiperspirants and perspiration absorbers. 6.Preparations as claimed in at least one of claims 1 to 5, characterizedin that they are present as a spray.
 7. Preparations as claimed in atleast one of claims 1 to 5, characterized in that they are present assticks.
 8. Preparations as claimed in at least one of claims 1 to 5,characterized in that they are present as roll-ons.
 9. Preparations asclaimed in at least one of claims 1 to 5, characterized in that they arepresent as emulsions.
 10. The use of nanoscale chitosans and/or chitosanderivatives with particle diameters of 10 to 300 nm in deodorizingpreparations.